EP0327423B1 - Polymers derived from unsaturated polyesters by addition of compounds having an amine function, and their use as additives to modify the properties in the cold state of middle distillates of petroleum - Google Patents

Polymers derived from unsaturated polyesters by addition of compounds having an amine function, and their use as additives to modify the properties in the cold state of middle distillates of petroleum Download PDF

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Publication number
EP0327423B1
EP0327423B1 EP89400181A EP89400181A EP0327423B1 EP 0327423 B1 EP0327423 B1 EP 0327423B1 EP 89400181 A EP89400181 A EP 89400181A EP 89400181 A EP89400181 A EP 89400181A EP 0327423 B1 EP0327423 B1 EP 0327423B1
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Prior art keywords
carbon atoms
compound
compounds
group
polymer according
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German (de)
French (fr)
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EP0327423A1 (en
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Jacques Denis
Jacques Garapon
Bernard Damin
Robert Léger
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Elf Antar France
IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
Elf France SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

Definitions

  • the present invention relates to modified polymers comprising amino-substituted side groups derived from compounds with a primary amine function.
  • the polymers of the present invention are in particular usable as additives allowing the improvement of the cold flow properties of petroleum middle distillates (fuels and gas oils).
  • the modified polymers of the present invention result from the reaction of at least one compound with a primary amine function corresponding to one of the general formulas (III) or (IV) described below, on a condensation polymer (unsaturated polyester) resulting from the condensation of at least one aliphatic unsaturated dicarboxylic compound, preferably vicinal, comprising at least one ethylenic unsaturation in alpha of one of the carboxylic groups (hereinafter called dicarboxylic compound) usually having from 4 to 60 carbon atoms , preferably from 4 to 30 carbon atoms and most often from 4 to 8 carbon atoms in its molecule, on at least one aliphatic epoxide (hereinafter called epoxidized compound) corresponding to one of the general formulas (I) or (II) described below.
  • a condensation polymer unsaturated polyester
  • dicarboxylic compound usually having from 4 to 60 carbon atoms , preferably from 4 to 30 carbon atoms and most often from 4 to 8 carbon
  • modified polymers of The present invention are additives allowing a significant improvement in the cold flow properties of middle hydrocarbon distillates, in particular an improvement in the pour point and / or the cloud point of gas oils.
  • condensation polymers used to prepare the modified polymers of the present invention are obtained by the conventional methods for preparing the condensation polymers well known to those skilled in the art.
  • the dicarboxylic compound which is used in the present invention is usually preferably a monounsaturated compound of 4 to 8 carbon atoms per molecule, for example maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and glutaconic acid.
  • the dicarboxylic compound is preferably a monounsaturated cyclic anhydride such as for example maleic anhydride, alkylmaleic anhydrides and alkenyl succinic anhydrides.
  • the preferred anhydrides are maleic anhydride, citraconic anhydride (methylmaleic) and itaconic anhydride (methylene-succinic).
  • the epoxidized compound used in the context of the present invention is a compound usually having from 4 to 62 carbon atoms, preferably from 4 to 40 carbon atoms, most often from 6 to 40 carbon atoms and advantageously from 8 to 40 carbon atoms in its molecule.
  • monoepoxidized compounds or mixtures of epoxidized compounds are preferably used, preferably comprising a proportion of at least 50 mol% of monoepoxidized compounds and containing compounds comprising several epoxy groups (oxirane rings) in their molecule, for example two or three epoxy groups.
  • the molar proportion of these compounds, called polyepoxide compounds, in the mixture of epoxidized compounds is usually less than 50%, preferably less than 40% and advantageously less than 30%.
  • the aliphatic epoxidized compounds used in the present invention correspond to one of the following general formulas: in which R1 and R3, identical or different, each represent a hydrogen atom or a lower alkyl group having for example from 1 to 4 carbon atoms, such as methyl, ethyl, propyls and butyls; R2 represents a hydrogen atom, an alkyl group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35 carbon atoms or an aliphatic group, preferably substantially linear, comprising one or more rings oxiranes in the chain and having from 3 to 57 carbon atoms, preferably from 3 to 35 carbon atoms and more particularly from 4 to 35 carbon atoms; R4 represents an alkylene group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35 carbon atoms; R5 represents an alkyl group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35
  • the preferred epoxidized compounds are those in which R1 and R3 each represent a hydrogen atom as well as those in which R1, R2 and R3 each represent a hydrogen atom.
  • R1 and R3 each represent a hydrogen atom and R2 represents a hydrogen atom, an alkyl group, preferably substantially linear, having from 6 to 35 atoms of carbon or an aliphatic group, preferably substantially linear, comprising one or more oxirane rings of formula in which R7 is an alkyl group, preferably substantially linear, having from 1 to 54 carbon atoms, preferably from 1 to 32 carbon atoms, R8 is an alkylene group, preferably substantially bonding, having from 1 to 54 carbon atoms carbon, preferably from 1 to 32 carbon atoms and q is an integer from 1 to 5, preferably from 1 to 3, the groups R4, R5 and R6 having the definitions given above.
  • aliphatic monoepoxide compounds As specific examples of aliphatic monoepoxide compounds, mention may be made of: 3-ethoxy-1,2-epoxy propane, 3-propoxy-1,2-epoxy propane, 3-butoxy-1,2-epoxy propane, 3-pentyloxy-1,2-epoxy propane, 3-hexyloxy 1,2-epoxy propane, heptyloxy-3 epoxy-1,2 propane, octyloxy-3 epoxy-1,2 propane, decyloxy-3 epoxy-1,2 propane, dodecyloxy-3 epoxy-1, 2 propane, acetoxy-1 epoxy-2,3 propane, butyryloxy-1 epoxy-2,3 propane, lauroyloxy-1 epoxy-2,3 propane, myristoyloxy-3 epoxy-1,2 propane, palmitoyloxy -3 1,2-epoxy propane, 3-stoyoyloxy-1,2-epoxy propane, alkyl esters, for example methyl, ethyl, propyl, butyl, 2-ethyl hex
  • mixtures of epoxy compounds comprising polyepoxides
  • the mixture of ethylenically unsaturated fatty acids is for example a mixture comprising, in approximate weight proportions given in Table I, below, acids having from 12 to 20 carbon atoms in their molecule and containing saturated and unsaturated acids. This mixture is usually called olein.
  • C p.1 denotes acids comprising ethylenic unsaturation
  • C p.2 denotes acids comprising 2 ethylenic unsaturations
  • C p.3 denotes acids comprising 3 ethylenic unsaturations
  • p is the number of atoms of carbon.
  • a mixture of alcohols is used, for example comprising, in approximate weight proportion, 95% of n-hexadecyl alcohols, 3% of n-octadecyl alcohol and 2% of alcohol having more of 18 carbon atoms in their molecule. It should be understood that it is possible to bring into play as epoxidized compound one or more compounds corresponding to formula (I) and / or one or more compounds corresponding to formula (II).
  • the unsaturated polyester is usually obtained by reacting at least one dicarboxylic compound (as defined above) with at least one epoxidized compound (as defined above) in the presence of a condensation catalyst, for example a strong acid or a titanium salt, for example an alkyl titanate, in particular n-butyl titanate.
  • a condensation catalyst for example a strong acid or a titanium salt, for example an alkyl titanate, in particular n-butyl titanate.
  • the condensation between at least one dicarboxylic compound and at least one epoxidized compound can be carried out in the presence or in the absence of solvent. It is possible for example to use a hydrocarbon solvent such as benzene, hexane, cyclohexane, toluene, xylene or a mixture of hydrocarbons such as for example a high boiling hydrocarbon fraction such as kerosene or diesel.
  • the condensation reaction is usually carried out at a temperature of about 30 to 200 ° C and preferably about 50 to 160 ° C for about 30 minutes to about 30 hours and preferably for about 2 hours to about 15 hours.
  • the condensation between the dicarboxylic compound and the epoxidized compound is carried out by using amounts of each of these compounds such that the epoxidized compound / dicarboxylic compound molar ratio is usually about 0.4: 1 to 1.8: 1 and preferably from about 0.8: 1 to about 1.2: 1 and more particularly from about 0.9: 1 to about 1.1: 1.
  • the unsaturated polyester thus obtained is then reacted with at least one compound with a primary amine function as defined below.
  • the reaction is usually carried out in the presence of a solvent which may be the same or different from that used in the step of preparing the unsaturated polyester.
  • the polyester is preferably first dissolved with an amount of solvent usually representing by weight the weight of the polyester formed, then the addition reaction is carried out with the compound containing a primary amine function. .
  • the primary amine function compounds which are used usually comprise from 1 to 61 carbon atoms, preferably from 6 to 47 carbon atoms and more particularly from 8 to 47 carbon atoms in their molecule.
  • These compounds with a primary amine function correspond to one of the following general formulas: (IV) HO - R10 - NH2 in which R9 represents an aliphatic group, having from 1 to 60 carbon atoms, preferably from 6 to 46 carbon atoms, preferably saturated; Z is chosen from the groups -O-, -NH- and -NR11-, in which R11 represents an aliphatic group, preferably saturated, having from 1 to 60 carbon atoms, preferably from 6 to 40 carbon atoms and preferably R11 is a substantially linear group; n is an integer from 2 to 4; m is zero when Z is -NH- or an integer from 1 to 4 in all cases; R10 represents an aliphatic group, preferably saturated, divalent having from 2 to 61 carbon atoms, preferably from 6 to 47
  • the compounds of formula (III) above can consist of primary monoalkylamines of formula R9-NH2 (in this case, in formula (I), Z represents the group -NH-, and the value of m is zero ).
  • the group R9 is substantially linear and contains from 6 to 46 carbon atoms and in a preferred manner from 8 to 46 carbon atoms and more advantageously from 10 to 46 carbon atoms.
  • these amines there may be mentioned, by way of examples: methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine , dodecylamine, tetradecylamine, hexadecylamine, octadecylamine; eicosylamine and docosylamine.
  • the compounds of formula (III) may also consist of preferably saturated aliphatic polyamines corresponding to the formula: which corresponds to the general formula (III) in which Z represents the group -NH-; m can have a value from 1 to 4 and n can have a value from 2 to 4, preferably 3.
  • R9 has the definition given above.
  • the number of carbon atoms in the polyamine used is usually from 3 to 61, preferably from 6 to 47, more particularly from 8 to 47 and more advantageously from 10 to 47.
  • N-alkyl diamino-1,3 propane in which the alkyl group contains from 5 to 24 carbon atoms and preferably from 7 to 24 carbon atoms for example N- dodecyl diamino-1,3 propane, N-tetradecyl diamino-1,3 propane, N-hexadecyl diamino-1,3 propane, N-octadecyl diamino-1,3 propane, N-eicosyl diamino-1,3 propane and N-docosyl diamino-1,3 propane; there may also be mentioned the N-alkyl dipropylene triamines in which the alkyl group contains from 2 to 24 carbon atoms and for example among the compounds in which the alkyl group contains from 12 to 24 carbon atoms, N-hexadecyldipropylene triamine, N -octadecyldipropylene triamine, N-eicosyldiprop
  • the compounds of formula (III) can also consist of polyamines corresponding to the formula: corresponding to the general formula (III) where Z represents -NR11- and where R9 and R11, identical or different, each representing an alkyl group having from 1 to 60 carbon atoms, preferably from 6 to 40 carbon atoms, R9 and R11 usually containing between them from 7 to 61 carbon atoms and preferably from 8 to 46 carbon atoms; na has an integer value from 2 to 4 and m an integer value from 1 to 4; R9 and R11 are preferably substantially linear.
  • Examples of specific compounds that may be mentioned include N, N-diethyl-1,2-diamino ethane, N, N-diisopropyl-1,2-diamino ethane, N, N-dibutyl diamino-1,2 ethane , N, N-diethyl-1,4-diamino butane, NN-dimethyl diamino-1,3 propane, N, N-diethyl diamino-1,3 propane, N, N-dioctyl diamino-1,3 propane , N, N-didecyl diamino-1,3 propane, N, N-didodécyl diamino-1,3 propane, N, N-dissetradécyl diamino-1,3 propane, N, N-dihexadécyl diamino-1, 3 propane, N, N-dioctadecyl diamino-1,3 propane, N,
  • the compounds of formula (III) can consist of ether-amines corresponding more particularly to the formula: which corresponds to the general formula (III) in which Z is an oxygen atom; preferably, the radical R9 is substantially linear and with the definition given above, m is an integer from 1 to 4 and n is an integer from 2 to 4, preferably 2 or 3.
  • alkyl ether amines that may be mentioned as examples of specific compounds: 2-methoxy-ethylamine, 3-methoxy-propylamine, 4-methoxy-butylamine, 3-ethoxypropylamine, 3-octyloxy propylamine, decyloxy-3 propylamine, hexadecyloxy-3 propylamine, eicosyloxy-3 propylamine, docosyloxy-3 propylamine, N- (3-octyloxy-propyl) diamino-1,3 propane, N- (decyloxy- 3 propyl) diamino-1,3 propane, (trimethyl-2,4,6 decyl) oxy-3 propylamine and N- (trimethyl-2,4,6 decyl) oxy-3 propyl diamino-1,3 propane.
  • the compound with a primary amine function involved in the preparation of the modified copolymers of the invention may also consist of an amino alcohol of formula (IV): HO - R10 - NH2 where R10 represents an aliphatic radical preferably saturated, divalent, linear or branched, preferably substantially linear, having the definition given above. Amino alcohols having a primary alcohol function are preferably used.
  • monoethanolamine amino-1 propanol-3, amino-1 butanol-4, amino-1 pentanol-5, amino-1 hexanol-6, amino-1 heptanol-7, amino-1 octanol-8, amino-1 decanol-10, amino-1 undecanol-11, amino-1 tridecanol-13, amino-1 tetradecanol-14, amino-1 hexadecanol- 16, 2-amino-2-methyl-propanol-1, 2-amino butanol-1 and 2-amino pentanol-1.
  • the addition reaction of the compound with primary amine function on the unsaturated polyester is usually carried out by simple heating at a temperature usually of about 25 to 200 ° C, preferably from 40 to 160 ° C and for example at about 60 ° C .
  • the reaction is carried out by adding the compound containing a primary amine function to the unsaturated polyester dissolved in a solvent chosen, for example, from those mentioned above, and heating, at the chosen temperature, for a time sufficient for the reaction to be substantially complete.
  • the reaction time between the primary amine functional compound and the unsaturated polyester is usually about 1 to 24 hours and most often about 2 to 10 hours and for example about 3 hours.
  • the quantity of compound with primary amine function reacted is usually from 0.2 to 1.5 mol, preferably from from 0.4 to 1.2 moles and most preferably from 0.5 to 1.1 moles per mole of dicarboxylic compound involved in the formation of the unsaturated polyester.
  • the amount of amine-functional compound is, for example, about 1 mole per 1 mole of dicarboxylic compound.
  • modified polymers of the present invention which can be advantageously used as additives in petroleum middle distillates are those which have substantially linear pendant side chains having at least 8 carbon atoms, preferably at least 10 carbon atoms and of a most preferably at least 12 carbon atoms, said chain possibly comprising oxygen and / or nitrogen atoms.
  • These side chains can come either from the epoxidized compound used in the preparation of the unsaturated polyester, or from the compound with primary amine function reacted with the unsaturated polyester, or from both the epoxidized compound and from the compound with primary amine function.
  • the modified polymers according to the invention used as additives in middle distillates are those which have pendant side chains having at least 8 carbon atoms and advantageously at least 10 carbon atoms and most preferably at least 12 carbon atoms, originating both from the epoxidized compound used in the preparation of the unsaturated polyester and from the compound with a primary amine function reacted with the unsaturated polyester.
  • the polymers modified according to the invention usually have a number-average molecular weight of about 400 to 20,000 and preferably about 500 to 10,000 and most often about 500 to 7,000.
  • the preferred modified polymers according to the invention make it possible to simultaneously have an improvement in the cloud point and the pour point of petroleum middle distillates, which makes them particularly attractive to the refiner.
  • the additives are obtained in solution in the chosen solvent and can be used in this form directly in petroleum middle distillates (for example in gas oils) for which it is desired to improve the pour point and the cloud point.
  • the gas oil compositions according to the invention comprise a major proportion of middle petroleum distillate having a distillation range according to the distillation standard ASTM D 8667 lying between 150 and 450 ° C. (fuels oils, gas oils) and a minor proportion, sufficient to lower the cloud point and the pour point simultaneously with at least one modified polymer defined above.
  • the gas oils considered more particularly have a distillation range from an initial temperature of about 160 to 190 ° C to a final temperature of about 360 to 430 ° C.
  • Diesel compositions comprising a major proportion of middle distillate and at least one additive chosen from the polymers modified according to the invention, defined above, in an amount sufficient to lower the cloud point and the pour point, may also include other additives such as for example antioxidant additives, additives dispersing sludge, corrosion inhibitors, etc.
  • compositions usually comprise at least 95% and preferably at least 98% by weight of middle distillate.
  • the lowering of the pour point can go, for example up to 15 ° C or more.
  • a decrease in the cloud point can simultaneously be observed, which can go, for example, up to 2 ° C. or more.
  • the modified polymers used in the invention allow, by their action on the kinetic phenomena of crystallization, in particular paraffins, and on the modification of the size of the crystals which form, the use of the suspension at a lower temperature without clogging of pipes, or clogging of filters.
  • paraffin crystals whose formation is caused by cooling have appeared, their natural tendency is to collect by gravity in the lower part.
  • This phenomenon known under the term sedimentation, causes the clogging of the pipes and the clogging of the filters and is detrimental to the proper use of middle distillates and in particular of domestic diesel and fuels at low temperature.
  • the modified polymers of the invention reduce the rate of sedimentation of the paraffins formed by cooling the gas oils and other middle distillates; the paraffins remaining more in suspension are deposited less on the walls of the pipes in contact with gas oils and other middle distillates, thus delaying the clogging of said pipes, and making it possible to use a product of given characteristics at a significantly lower temperature or using a product at a given temperature, which obtained by the refiner without modifying the distillation scheme does not initially have the required specifications; specifications which are currently evolving in the direction of greater severity.
  • gas oil cuts used are those which appear in Table II; they are characterized according to the distillation ASTM D 8667, these cuts of diesel oils of ARAMCO origin are designated by G1 and G2; their density is also indicated in Table II.
  • the polymer obtained is diluted to 50% by weight in xylene; this solution constitutes the mother solution of additive A.
  • Example 1 The same solution of the same polyester as that described in Example 1 is prepared in the same manner as in Example 1 and the procedure is carried out on various parts of this unsaturated polyester to the addition of compounds having primary amine functions.
  • a solution of a product which, after evaporation of the solvent, can be characterized by conventional means of analysis: its number average molecular mass is 6,500, its polydispersity is 1.2 (measured by Steric Exclusion Chromatography (CES)), the NMR spectrum shows the disappearance of the unsaturation and confirms the addition of the amine to the double bond; in infrared spectrometry, the disappearance of the band corresponding to the ethylenic unsaturation of the starting polymer is also noted.
  • the solution obtained is diluted so as to obtain a 50% by weight solution in xylene, of the product, which constitutes the mother solution of the additive A1.
  • the cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles 3% of C8, 6% of C10, 56% of C12, 18% of C14, 10% of C16, 2 % of C18, and 5% of unsaturated C18.
  • the operating mode is in all respects identical to that described in Example 2.
  • the IR and NMR spectra of the product have the same characteristic bands as those of the additive A1.
  • a solution of the additive A2 is thus obtained.
  • Additive A2 has a number average molecular weight of 4,700 and its polydispersity is 1.33 (measured by CES).
  • the cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles 1% of C14, 5% of C16, 42% of C18, 12% of C20 and 40% of C22.
  • the procedure is identical in all respects to that described in Example 2.
  • the IR and NMR spectra of the product have the same characteristic bands as those of the additive A1.
  • a solution of the additive A3 is thus obtained.
  • Additive A3 has a number average molecular weight of 6,300 and its polydispersity is 1.2 (measured by C.E.S).
  • An unsaturated polyester is prepared in the same manner as in Example 1, which differs from that of Example 1 in that a cut of hexadecyl epoxystearate is used as the epoxidized compound.
  • This section was obtained by epoxidation of olein (mixture of unsaturated fatty acids whose average composition by weight is given in table I of the text of the present application) then esterification of the mixture of epoxy-acids obtained by a mixture of 'Alcohols comprising in approximate weight proportions 95% of n-hexadecyl alcohol, 3% of n-octadecyl alcohol and 2% of alcohol having more than 18 carbon atoms in their molecule. After diluting to 50% by weight in xylene, a solution of additive B is obtained.
  • Example 5 The same solution is prepared in the same manner as in Example 5, the same polyester as that described in Example 5, and various compounds of this unsaturated polyester are added to the compounds having primary amine functions, following the procedure described in Example 2 and respecting the molar proportions of Example 2.
  • the infrared and NMR spectra confirm the structure of the products and in particular the addition of the primary amino compounds to the double bond.
  • the primary amine added to the polyester is n-octadecylamine. A solution of the additive B1 is thus obtained.
  • the cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles: 1% of C14, 28% of C16 and 71% of C18.
  • a solution of the additive B2 is thus obtained.
  • Additive B2 has a number average molecular weight of 2,800 and its polydispersity is 1.65 (measured by C.E.S.)
  • the cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately: 3% of C8, 6% of C10, 56% of C12, 18% of C14, 10% of C%, 2% of C18 and 5% of unsaturated C18.
  • a solution of the additive B3 is thus obtained.
  • Additive B3 has a number average molecular weight of 2600 and its polydispersity is 1.72 (measured by C.E.S.).
  • the cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles: 1% of C14, 5% of C16, 42% of C18, 12% of C20 and 40% of C22.
  • a solution of the additive B4 is thus obtained.
  • Additive B4 has a number average molecular weight of 2,200 and its polydispersity is 2.15 (measured by C.E.S.).
  • the additives described above are obtained in solution in xylene.
  • the concentration of the solutions is adjusted to 50% by weight of dry matter, which provides the stock solutions of these additives, the activity of which is tested by incorporating them at a rate of 0.1% by weight relative to the diesel fuel, the characteristics of which have been given in table II above.

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Description

La présente invention concerne des polymères modifiés comportant des groupements latéraux amino-substitués dérivés de composés à fonction amine primaire.The present invention relates to modified polymers comprising amino-substituted side groups derived from compounds with a primary amine function.

Les polymères de la présente invention sont en particulier utilisables comme additifs permettant l'amélioration des propriétés d'écoulement à froid des distillats moyens de pétrole (fuels et gazoles).The polymers of the present invention are in particular usable as additives allowing the improvement of the cold flow properties of petroleum middle distillates (fuels and gas oils).

Les polymères modifiés de la présente invention résultent de la réaction d'au moins un composé à fonction amine primaire répondant à l'une des formules générales (III) ou (IV) décrites ci-après, sur un polymère de condensation (polyester insaturé) résultant de la condensation d'au moins un composé aliphatique insaturé dicarboxylique, de préférence vicinal, comportant au moins une insaturation éthylénique en alpha de l'un des groupes carboxyliques (dénommé ci-après composé dicarboxylique) ayant habituellement de 4 à 60 atomes de carbone, de préférence de 4 à 30 atomes de carbone et le plus souvent de 4 à 8 atomes de carbone dans sa molécule, sur au moins un époxyde aliphatique (dénommé ci-après composé époxydé) répondant à l'une des formules générales (I) ou (II) décrites ci-après.The modified polymers of the present invention result from the reaction of at least one compound with a primary amine function corresponding to one of the general formulas (III) or (IV) described below, on a condensation polymer (unsaturated polyester) resulting from the condensation of at least one aliphatic unsaturated dicarboxylic compound, preferably vicinal, comprising at least one ethylenic unsaturation in alpha of one of the carboxylic groups (hereinafter called dicarboxylic compound) usually having from 4 to 60 carbon atoms , preferably from 4 to 30 carbon atoms and most often from 4 to 8 carbon atoms in its molecule, on at least one aliphatic epoxide (hereinafter called epoxidized compound) corresponding to one of the general formulas (I) or (II) described below.

On a découvert, de façon surprenante, que les polymères modifiés de la présente invention sont des additifs permettant une amélioration importante des propriétés d'écoulement à froid des distillats moyens d'hydrocarbures, en particulier une amélioration du point d'écoulement et/ou du point de trouble des gazoles.It has surprisingly been found that the modified polymers of The present invention are additives allowing a significant improvement in the cold flow properties of middle hydrocarbon distillates, in particular an improvement in the pour point and / or the cloud point of gas oils.

Les polymères de condensation servant à préparer les polymères modifiés de la présente invention sont obtenus par les méthodes classiques de préparation des polymères de condensation bien connues de l'homme du métier.The condensation polymers used to prepare the modified polymers of the present invention are obtained by the conventional methods for preparing the condensation polymers well known to those skilled in the art.

Le composé dicarboxylique que l'on emploie dans la présente invention est habituellement, de préférence, un composé monoinsaturé de 4 à 8 atomes de carbone par molécule, par exemple l'acide maléique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide mésaconique et l'acide glutaconique.The dicarboxylic compound which is used in the present invention is usually preferably a monounsaturated compound of 4 to 8 carbon atoms per molecule, for example maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and glutaconic acid.

Le composé dicarboxylique est de préférence un anhydride cyclique monoinsaturé tel que par exemple l'anhydride maléique, les anhydrides alkylmaléiques et les anhydrides alcényl-succiniques.The dicarboxylic compound is preferably a monounsaturated cyclic anhydride such as for example maleic anhydride, alkylmaleic anhydrides and alkenyl succinic anhydrides.

Dans le cadre de l'invention, les anhydrides préférés sont l'anhydride maléique, l'anhydride citraconique (méthylmaléique) et l'anhydride itaconique (méthylène-succinique).In the context of the invention, the preferred anhydrides are maleic anhydride, citraconic anhydride (methylmaleic) and itaconic anhydride (methylene-succinic).

Le composé époxydé utilisé dans le cadre de la présente invention est un composé ayant habituellement de 4 à 62 atomes de carbone, de préférence de 4 à 40 atomes de carbone, le plus souvent de 6 à 40 atomes de carbone et avantageusement de 8 à 40 atomes de carbone dans sa molécule.The epoxidized compound used in the context of the present invention is a compound usually having from 4 to 62 carbon atoms, preferably from 4 to 40 carbon atoms, most often from 6 to 40 carbon atoms and advantageously from 8 to 40 carbon atoms in its molecule.

Dans le cadre de la présente invention on utilise de préférence des composés monoépoxydés ou des mélanges de composés époxydés comprenant de préférence une proportion d'au moins 50 % en mole de composés monoépoxydés et contenant des composés comprenant plusieurs groupes époxydes (cycles oxirannes) dans leur molécule, par exemple deux ou trois groupes époxydes. La proportion molaire de ces composés, dénommés composés polyépoxydés, dans le mélange des composés époxydés est habituellement inférieure à 50 %, de préférence inférieure à 40 % et de manière avantageuse inférieure à 30 %.In the context of the present invention, monoepoxidized compounds or mixtures of epoxidized compounds are preferably used, preferably comprising a proportion of at least 50 mol% of monoepoxidized compounds and containing compounds comprising several epoxy groups (oxirane rings) in their molecule, for example two or three epoxy groups. The molar proportion of these compounds, called polyepoxide compounds, in the mixture of epoxidized compounds is usually less than 50%, preferably less than 40% and advantageously less than 30%.

Les composés époxydés aliphatiques utilisés dans la présente invention répondent à l'une des formules générales suivantes :

Figure imgb0001

dans lesquelles R¹ et R³, identiques ou différents, représentent chacun un atome d'hydrogène ou un groupe alkyle inférieur ayant par exemple de 1 à 4 atomes de carbone, tel que méthyle, éthyle, propyles et butyles ; R² représente un atome d'hydrogène, un groupe alkyle, de préférence sensiblement linéaire, ayant de 1 à 57 atomes de carbone, de préférence de 1 à 35 atomes de carbone ou un groupe aliphatique, de préférence sensiblement linéaire, comportant un ou plusieurs cycles oxirannes dans la chaîne et ayant de 3 à 57 atomes de carbone, de préférence de 3 à 35 atomes de carbone et plus particulièrement de 4 à 35 atomes de carbone ; R⁴ représente un groupe alkylène, de préférence sensiblement linéaire, ayant de 1 à 57 atomes de carbone, de préférence de 1 à 35 atomes de carbone ; R⁵ représente un groupe alkyle, de préférence sensiblement linéaire, ayant de 1 à 57 atomes de carbone, de préférence de 1 à 35 atomes de carbone et plus particulièrement de 4 à 35 atomes de carbone ou un groupe alkanoyle, de formule R⁶-C- ; R⁶ représente dans ces formules un groupe alkyle, de préférence sensiblement linéaire, ayant de 1 à 56 atomes de carbone, de préférence de 1 à 34 atomes de carbone et plus particulièrement de 4 à 34 atomes de carbone.The aliphatic epoxidized compounds used in the present invention correspond to one of the following general formulas:
Figure imgb0001
in which R¹ and R³, identical or different, each represent a hydrogen atom or a lower alkyl group having for example from 1 to 4 carbon atoms, such as methyl, ethyl, propyls and butyls; R² represents a hydrogen atom, an alkyl group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35 carbon atoms or an aliphatic group, preferably substantially linear, comprising one or more rings oxiranes in the chain and having from 3 to 57 carbon atoms, preferably from 3 to 35 carbon atoms and more particularly from 4 to 35 carbon atoms; R⁴ represents an alkylene group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35 carbon atoms; R⁵ represents an alkyl group, preferably substantially linear, having from 1 to 57 carbon atoms, preferably from 1 to 35 carbon atoms and more particularly from 4 to 35 carbon atoms or an alkanoyl group, of formula R⁶-C- ; R⁶ represents in these formulas an alkyl group, preferably substantially linear, having from 1 to 56 carbon atoms, preferably from 1 to 34 carbon atoms and more particularly from 4 to 34 carbon atoms.

Les composés époxydés préférés sont ceux dans lesquels R¹ et R³ représentent chacun un atome d'hydrogène ainsi que ceux dans lesquels R¹, R² et R³ représentent chacun un atome d'hydrogène.The preferred epoxidized compounds are those in which R¹ and R³ each represent a hydrogen atom as well as those in which R¹, R² and R³ each represent a hydrogen atom.

A titre d'exemples de composés époxydés préférés on peut citer les composés dans lesquels R¹ et R³ représentent chacun un atome d'hydrogène et R² représente un atome d'hydrogène, un groupe alkyle, de préférence sensiblement linéaire ayant de 6 à 35 atomes de carbone ou un groupe aliphatique, de préférence sensiblement linéaire, comportant un ou plusieurs cycles oxirannes de formule

Figure imgb0002

dans laquelle R⁷ est un groupe alkyle, de préférence sensiblement linéaire, ayant de 1 à 54 atomes de carbone, de préférence de 1 à 32 atomes de carbone, R⁸ est un groupe alkylène, de préférence sensiblement liénaire, ayant de 1 à 54 atomes de carbone, de préférence de 1 à 32 atomes de carbone et q est un nombre entier de 1 à 5, de préférence de 1 à 3, les groupes R⁴, R⁵ et R⁶ ayant les définitions données ci-avant.As examples of preferred epoxy compounds, mention may be made of the compounds in which R¹ and R³ each represent a hydrogen atom and R² represents a hydrogen atom, an alkyl group, preferably substantially linear, having from 6 to 35 atoms of carbon or an aliphatic group, preferably substantially linear, comprising one or more oxirane rings of formula
Figure imgb0002
in which R⁷ is an alkyl group, preferably substantially linear, having from 1 to 54 carbon atoms, preferably from 1 to 32 carbon atoms, R⁸ is an alkylene group, preferably substantially bonding, having from 1 to 54 carbon atoms carbon, preferably from 1 to 32 carbon atoms and q is an integer from 1 to 5, preferably from 1 to 3, the groups R⁴, R⁵ and R⁶ having the definitions given above.

A titre de composés préférés, parmi ceux mentionnés ci-avant, on peut citer les composés époxydés de formule (I) dans lesquels R⁴ représente un groupe méthylène et les composés époxydés de formule (II) dans lesquels R⁴ représente un groupe alkylène ayant de 4 à 24 atomes de carbone.As preferred compounds, among those mentioned above, there may be mentioned the epoxidized compounds of formula (I) in which R⁴ represents a methylene group and the epoxidized compounds of formula (II) in which R⁴ represents an alkylene group having 4 to 24 carbon atoms.

A titre d'exemples spécifiques de composés monoépoxydés aliphatiques on peut citer :
l'éthoxy-3 époxy-1,2 propane, le propoxy-3 époxy-1,2 propane, le butoxy-3 époxy-1,2 propane, le pentyloxy-3 époxy-1,2 propane, l'hexyloxy-3 époxy-1,2 propane, l'heptyloxy-3 époxy-1,2 propane, l'octyloxy-3 époxy-1,2 propane, le décyloxy-3 époxy-1,2 propane, le dodécyloxy-3 époxy-1,2 propane, l'acétoxy-1 époxy-2,3 propane, le butyryloxy-1 époxy-2,3 propane, le lauroyloxy-1 époxy-2,3 propane, le myristoyloxy-3 époxy-1,2 propane, le palmitoyloxy-3 époxy-1,2 propane, le stéaroyloxy-3 époxy-1,2 propane, les esters alkyliques, par exemple méthylique, éthylique, propyliques, butyliques, éthyl-2 hexylique et et hexadécyliques des acides époxy-3,4 butanoïque, époxy-4,5 pentanoïque, époxy-3,4 nonanoïque, époxy-10,11 undécanoïque, époxy-6,7 octadécanoïque, époxy-12,13 octadécanoïque, époxy-11,12 octadécanoïque, époxy-9,10 octadécanoïque, époxy-11,12 eicosanoïque et époxy-13,14 docosanoïque.As specific examples of aliphatic monoepoxide compounds, mention may be made of:
3-ethoxy-1,2-epoxy propane, 3-propoxy-1,2-epoxy propane, 3-butoxy-1,2-epoxy propane, 3-pentyloxy-1,2-epoxy propane, 3-hexyloxy 1,2-epoxy propane, heptyloxy-3 epoxy-1,2 propane, octyloxy-3 epoxy-1,2 propane, decyloxy-3 epoxy-1,2 propane, dodecyloxy-3 epoxy-1, 2 propane, acetoxy-1 epoxy-2,3 propane, butyryloxy-1 epoxy-2,3 propane, lauroyloxy-1 epoxy-2,3 propane, myristoyloxy-3 epoxy-1,2 propane, palmitoyloxy -3 1,2-epoxy propane, 3-stoyoyloxy-1,2-epoxy propane, alkyl esters, for example methyl, ethyl, propyl, butyl, 2-ethyl hexyl and and hexadecyls of epoxy-3,4 butanoic, epoxy-4,5 pentanoic, epoxy-3,4 nonanoic, epoxy-10,11 undecanoic, epoxy-6,7 octadecanoic, epoxy-12,13 octadecanoic, epoxy-11, 12 octadecanoic, epoxy-9.10 octadecanoic, epoxy-11.12 eicosanoic and epoxy-13.14 docosanoic.

A titre d'exemples spécifiques de mélanges de composés époxydés comprenant des polyépoxydes on peut citer le mélange d'esters alkyliques obtenu par estérification d'un mélange d'époxyacides résultant de l'époxydation d'un mélange d'acides gras éthyléniquement insaturés. Le mélange d'acides gras éthyléniquement insaturés est par exemple un mélange comportant, en proportions pondérales approximatives données dans le tableau I, ci-après, des acides ayant de 12 à 20 atomes de carbone dans leur molécule et contenant des acides saturés et insaturés. Ce mélange est habituellement dénommé oléine.

Figure imgb0003
As specific examples of mixtures of epoxy compounds comprising polyepoxides, mention may be made of the mixture of alkyl esters obtained by esterification of a mixture of epoxy acids resulting from the epoxidation of a mixture of ethylenically unsaturated fatty acids. The mixture of ethylenically unsaturated fatty acids is for example a mixture comprising, in approximate weight proportions given in Table I, below, acids having from 12 to 20 carbon atoms in their molecule and containing saturated and unsaturated acids. This mixture is usually called olein.
Figure imgb0003

Dans le tableau I ci-avant Cp.1 désigne des acides comportant une insaturation éthylénique, Cp.2 désigne des acides comportant 2 insaturations éthyléniques et Cp.3 désigne des acides comportant 3 insaturations éthyléniques (p est le nombre d'atomes de carbone).
Pour l'estérification du mélange d'époxyacides on utilise par exemple un mélange d'alcools comprenant, en proportion pondérales approximatives, 95 % d'alcools n-hexadécylique, 3 % d'alcool n-octadécylique et 2 % d'alcool ayant plus de 18 atomes de carbone dans leur molécule. Il doit être entendu qu'il est possible de mettre en jeu comme composé époxydé un ou plusieurs composés répondant à la formule (I) et/ou un ou plusieurs composés répondant à la formule (II).In Table I above, C p.1 denotes acids comprising ethylenic unsaturation, C p.2 denotes acids comprising 2 ethylenic unsaturations and C p.3 denotes acids comprising 3 ethylenic unsaturations (p is the number of atoms of carbon).
For the esterification of the mixture of epoxy acids, a mixture of alcohols is used, for example comprising, in approximate weight proportion, 95% of n-hexadecyl alcohols, 3% of n-octadecyl alcohol and 2% of alcohol having more of 18 carbon atoms in their molecule. It should be understood that it is possible to bring into play as epoxidized compound one or more compounds corresponding to formula (I) and / or one or more compounds corresponding to formula (II).

Le polyester insaturé est habituellement obtenu en faisant réagir au moins un composé dicarboxylique (tel que défini ci-dessus) avec au moins un composé époxydé (tel que défini ci-dessus) en présence d'un catalyseur de condensation, par exemple un acide fort ou un sel de titane par exemple un titanate d'alkyle en particulier le titanate de n-butyle.The unsaturated polyester is usually obtained by reacting at least one dicarboxylic compound (as defined above) with at least one epoxidized compound (as defined above) in the presence of a condensation catalyst, for example a strong acid or a titanium salt, for example an alkyl titanate, in particular n-butyl titanate.

La condensation entre au moins en composé dicarboxylique et au moins un composé époxydé peut être effectuée en présence ou en absence de solvant. On peut par exemple utiliser un solvant hydrocarboné tel que le benzène, l'hexane, le cyclohexane, le toluène, le xylène ou un mélange d'hydrocarbures tel que par exemple une coupe hydrocarbonée à point d'ébullition élevé telle qu'un kérosène ou un gazole.
La réaction de condensation est habituellement effectuée à une température d'environ 30 à 200 °C et de préférence d'environ 50 à 160 °C pendant environ 30 minutes à environ 30 heures et de préférence pendant environ 2 heures à environ 15 heures.The condensation between at least one dicarboxylic compound and at least one epoxidized compound can be carried out in the presence or in the absence of solvent. It is possible for example to use a hydrocarbon solvent such as benzene, hexane, cyclohexane, toluene, xylene or a mixture of hydrocarbons such as for example a high boiling hydrocarbon fraction such as kerosene or diesel.
The condensation reaction is usually carried out at a temperature of about 30 to 200 ° C and preferably about 50 to 160 ° C for about 30 minutes to about 30 hours and preferably for about 2 hours to about 15 hours.

La condensation entre la composé dicarboxylique et le composé époxydé est effectuée en employant des quantités de chacun de ces composés telles que le rapport molaire composé époxydé/composé dicarboxylique soit habituellement d'environ 0,4:1 à 1,8:1 et de préférence d'environ 0,8:1 à environ 1,2:1 et plus particulièrement d'environ 0,9:1 à environ 1,1:1.The condensation between the dicarboxylic compound and the epoxidized compound is carried out by using amounts of each of these compounds such that the epoxidized compound / dicarboxylic compound molar ratio is usually about 0.4: 1 to 1.8: 1 and preferably from about 0.8: 1 to about 1.2: 1 and more particularly from about 0.9: 1 to about 1.1: 1.

Le polyester insaturé, ainsi obtenu, est ensuite mis en réaction avec au moins un composé à fonction amine primaire tel que défini ci-après. La réaction est habituellement effectuée en présence d'un solvant qui peut être identique ou différent de celui utilisé dans l'étape de préparation du polyester insaturé.The unsaturated polyester thus obtained is then reacted with at least one compound with a primary amine function as defined below. The reaction is usually carried out in the presence of a solvent which may be the same or different from that used in the step of preparing the unsaturated polyester.

Lorsque le solvant utilisé dans cette réaction d'addition du composé à fonction amine est le même que celui employé lors de la formation du polyester, il est possible de ne pas isoler le polyester et d'effectuer la réaction sur le produit brut de polycondensation, éventuellement après avoir enlevé le catalyseur employé pour la polycondensation.When the solvent used in this reaction for adding the amine-functional compound is the same as that used during the formation of the polyester, it is possible not to isolate the polyester and to carry out the reaction on the crude polycondensation product, possibly after removing the catalyst used for the polycondensation.

Lorsque la polycondensation a été effectuée sans employer de solvant, le polyester est de préférence d'abord dissous avec une quantité de solvant représentant habituellement en poids le poids du polyester formé, puis on effectue la réaction d'addition avec le composé à fonction amine primaire.When the polycondensation has been carried out without using a solvent, the polyester is preferably first dissolved with an amount of solvent usually representing by weight the weight of the polyester formed, then the addition reaction is carried out with the compound containing a primary amine function. .

Les composés à fonction amine primaire que l'on utilise comprennent habituellement de 1 à 61 atomes de carbone, de préférence de 6 à 47 atomes de carbone et plus particulièrement de 8 à 47 atomes de carbone dans leur molécule. Ces composés à fonction amine primaire répondent à l'une des formules générales suivantes :

Figure imgb0004



        (IV)   HO - R¹⁰ - NH₂



dans lesquelles R⁹ représente un groupe aliphatique, ayant de 1 à 60 atomes de carbone, de préférence de 6 à 46 atomes de carbone, de préférence saturé ; Z est choisi parmi les groupes -O-, -NH- et -NR¹¹-, dans lesquels R¹¹ représente un groupe aliphatique, de préférence saturé, ayant de 1 à 60 atomes de carbone, de préférence de 6 à 40 atomes de carbone et préférentiellement R¹¹ est un groupe sensiblement linéaire ; n est un nombre entier de 2 à 4 ; m est zéro lorsque Z est -NH- ou un nombre entier de 1 à 4 dans tous les cas ; R¹⁰ représente un groupe aliphatique, de préférence saturé, divalent ayant de 2 à 61 atomes de carbone, de préférence de 6 à 47 atomes de carbone et plus particulièrement de 8 à 47 atomes de carbone.The primary amine function compounds which are used usually comprise from 1 to 61 carbon atoms, preferably from 6 to 47 carbon atoms and more particularly from 8 to 47 carbon atoms in their molecule. These compounds with a primary amine function correspond to one of the following general formulas:
Figure imgb0004


(IV) HO - R¹⁰ - NH₂



in which R⁹ represents an aliphatic group, having from 1 to 60 carbon atoms, preferably from 6 to 46 carbon atoms, preferably saturated; Z is chosen from the groups -O-, -NH- and -NR¹¹-, in which R¹¹ represents an aliphatic group, preferably saturated, having from 1 to 60 carbon atoms, preferably from 6 to 40 carbon atoms and preferably R¹¹ is a substantially linear group; n is an integer from 2 to 4; m is zero when Z is -NH- or an integer from 1 to 4 in all cases; R¹⁰ represents an aliphatic group, preferably saturated, divalent having from 2 to 61 carbon atoms, preferably from 6 to 47 carbon atoms and more particularly from 8 to 47 carbon atoms.

Les composés de formule (III) ci-dessus peuvent consister en des monoalkyl-amines primaires de formule R⁹-NH₂ (dans ce cas, dans la formule (I), Z représente le groupement -NH-, et la valeur de m est zéro).
De préférence le groupe R⁹ est sensiblement linéaire et renferme de 6 à 46 atomes de carbone et d'une manière préférée de 8 à 46 atomes de carbone et plus avantageusement de 10 à 46 atomes de carbone.The compounds of formula (III) above can consist of primary monoalkylamines of formula R⁹-NH₂ (in this case, in formula (I), Z represents the group -NH-, and the value of m is zero ).
Preferably the group R⁹ is substantially linear and contains from 6 to 46 carbon atoms and in a preferred manner from 8 to 46 carbon atoms and more advantageously from 10 to 46 carbon atoms.

Comme exemples spécifiques de ces amines, on peut citer, à titre d'exemples : la méthylamine, l'éthylamine, la propylamine, la butylamine, la pentylamine, l'hexylamine, l'heptylamine, l'octylamine, la nonylamine, la décylamine, la dodécylamine, la tétradécylamine, l'hexadecylamine, l'octadécylamine; l'éicosylamine et la docosylamine.As specific examples of these amines, there may be mentioned, by way of examples: methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine , dodecylamine, tetradecylamine, hexadecylamine, octadecylamine; eicosylamine and docosylamine.

Les composés de formule (III) peuvent encore consister en des polyamines aliphatiques de préférence saturées répondant à la formule :

Figure imgb0005

qui correspond à la formule générale (III) dans laquelle Z représente le groupement -NH- ; m peut avoir une valeur de 1 à 4 et n une valeur de 2 à 4, de préférence 3.
R⁹ a la définition donnée ci-avant. Le nombre d'atomes de carbone de la polyamine employée etant habituellement de 3 à 61, de préférence de 6 à 47, plus particulièrement de 8 à 47 et plus avantageusement de 10 à 47.The compounds of formula (III) may also consist of preferably saturated aliphatic polyamines corresponding to the formula:
Figure imgb0005
which corresponds to the general formula (III) in which Z represents the group -NH-; m can have a value from 1 to 4 and n can have a value from 2 to 4, preferably 3.
R⁹ has the definition given above. The number of carbon atoms in the polyamine used is usually from 3 to 61, preferably from 6 to 47, more particularly from 8 to 47 and more advantageously from 10 to 47.

Comme composés spécifiques, on peut citer à titre d'exemples les N-alkyl diamino-1,3 propane dans lesquels le groupe alkyle comporte de 5 à 24 atomes de carbone et de préférence de 7 à 24 atomes de carbone par exemple le N-dodécyl diamino-1,3 propane, le N-tétradécyl diamino-1,3 propane, le N-hexadécyl diamino-1,3 propane, le N-octadécyl diamino-1,3 propane, le N-eicosyl diamino-1,3 propane et le N-docosyl diamino-1,3 propane ; on peut également citer les N-alkyl dipropylène triamines dans lesquelles le groupe alkyle comporte de 2 à 24 atomes de carbone et par exemple parmi les composés dont le groupe alkyle comporte de 12 à 24 atomes de carbone, la N-hexadécyldipropylène triamine, la N-octadécyldipropylène triamine, la N-eicosyldipropylène triamine et la N-docosyldipropylène triamine.As specific compounds, there may be mentioned as examples the N-alkyl diamino-1,3 propane in which the alkyl group contains from 5 to 24 carbon atoms and preferably from 7 to 24 carbon atoms for example N- dodecyl diamino-1,3 propane, N-tetradecyl diamino-1,3 propane, N-hexadecyl diamino-1,3 propane, N-octadecyl diamino-1,3 propane, N-eicosyl diamino-1,3 propane and N-docosyl diamino-1,3 propane; there may also be mentioned the N-alkyl dipropylene triamines in which the alkyl group contains from 2 to 24 carbon atoms and for example among the compounds in which the alkyl group contains from 12 to 24 carbon atoms, N-hexadecyldipropylene triamine, N -octadecyldipropylene triamine, N-eicosyldipropylene triamine and N-docosyldipropylene triamine.

Les composés de formule (III) peuvent également consister en des polyamines répondant à la formule :

Figure imgb0006

correspondant à la formule générale (III) où Z représente -NR¹¹- et où R⁹ et R¹¹, identiques ou différents, représentant chacun un groupe alkyle ayant de 1 à 60 atomes de carbone, de préférence de 6 à 40 atomes de carbone, R⁹ et R¹¹ renfermant habituellement à eux deux de 7 à 61 atomes de carbone et de préférence de 8 à 46 atomes de carbone ; n a une valeur entière de 2 à 4 et m une valeur entière de 1 à 4 ; R⁹ et R¹¹ sont de préférence sensiblement linéaires.The compounds of formula (III) can also consist of polyamines corresponding to the formula:
Figure imgb0006
corresponding to the general formula (III) where Z represents -NR¹¹- and where R⁹ and R¹¹, identical or different, each representing an alkyl group having from 1 to 60 carbon atoms, preferably from 6 to 40 carbon atoms, R⁹ and R¹¹ usually containing between them from 7 to 61 carbon atoms and preferably from 8 to 46 carbon atoms; na has an integer value from 2 to 4 and m an integer value from 1 to 4; R⁹ and R¹¹ are preferably substantially linear.

Comme composés spécifiques, on peut citer à titre d'exemples le N,N-diéthyl diamino-1,2 éthane, le N,N-diisopropyl diamino-1,2 éthane, le N,N-dibutyl diamino-1,2 éthane, le N,N-diéthyl diamino-1,4 butane, le N-N-diméthyl diamino-1,3 propane, le N,N-diéthyl diamino-1,3 propane, le N,N-dioctyl diamino-1,3 propane, le N,N-didécyl diamino-1,3 propane, le N,N-didodécyl diamino-1,3 propane, le N,N-ditétradécyl diamino-1,3 propane, le N,N-dihexadécyl diamino-1,3 propane, le N,N-dioctadécyl diamino-1,3 propane, la N,N-didodécyldipropylène triamine, la N,N-ditétradécyldipropylène triamine, la N,N-dihexadécyldipropylène triamine, la N,N-dioctadécyldipropylène triamine, le N-méthyl N-butyl diamino-1,2 éthane, le N-méthyl N-octyl diamino-1,2 éthane, le N-éthyl N-octyl diamino-1,2 éthane, le N-méthyl N-décyl diamino-1,2 éthane, le N-méthyl N-dodécyl diamino 1,3 propane, le N-méthyl N-hexadécyl diamino-1,3 propane et le N-éthyl N-octadécyl diamino-1,3 propane.Examples of specific compounds that may be mentioned include N, N-diethyl-1,2-diamino ethane, N, N-diisopropyl-1,2-diamino ethane, N, N-dibutyl diamino-1,2 ethane , N, N-diethyl-1,4-diamino butane, NN-dimethyl diamino-1,3 propane, N, N-diethyl diamino-1,3 propane, N, N-dioctyl diamino-1,3 propane , N, N-didecyl diamino-1,3 propane, N, N-didodécyl diamino-1,3 propane, N, N-ditétradécyl diamino-1,3 propane, N, N-dihexadécyl diamino-1, 3 propane, N, N-dioctadecyl diamino-1,3 propane, N, N-didodecyldipropylene triamine, N, N-ditetradecyldipropylene triamine, N, N-dihexadecyldipropylene triamine, N, N-dioctadecyldipropylene triamine, N -methyl N-butyl diamino-1,2 ethane, N-methyl N-octyl diamino-1,2 ethane, N-ethyl N-octyl diamino-1,2 ethane, N-methyl N-decyl diamino-1 , 2 ethane, N-methyl N-dodecyl diamino 1,3 propane, N-methyl N-hexadecyl diamino-1,3 propane and N-ethyl N-octadecyl diamino-1,3 propane.

Enfin, les composés de formule (III) peuvent consister en des éther-amines répondant plus particulièrement à la formule :

Figure imgb0007

qui correspond à la formule générale (III) dans laquelle Z est un atome d'oxygène ; de préférence, le radical R⁹ est sensiblement linéaire et a la définition donnée ci-avant, m est un nombre entier de 1 à 4 et n un nombre entier de 2 à 4, préférentiellement 2 ou 3.Finally, the compounds of formula (III) can consist of ether-amines corresponding more particularly to the formula:
Figure imgb0007
which corresponds to the general formula (III) in which Z is an oxygen atom; preferably, the radical R⁹ is substantially linear and with the definition given above, m is an integer from 1 to 4 and n is an integer from 2 to 4, preferably 2 or 3.

Parmi les alkyl-éther-amines, on peut citer à titre d'exemples de composés spécifiques : la méthoxy-2 éthylamine, la méthoxy-3 propylamine, la méthoxy-4 butylamine, l'éthoxy-3 propylamine, l'octyloxy-3 propylamine, la décyloxy-3 propylamine, l'hexadécyloxy-3 propylamine, l'éicosyloxy-3 propylamine, la docosyloxy-3 propylamine, le N-(octyloxy-3 propyl) diamino-1,3 propane, le N-(décyloxy-3 propyl) diamino-1,3 propane, la (triméthyl-2,4,6 décyl) oxy-3 propylamine et le N- (triméthyl-2,4,6 décyl) oxy-3 propyl diamino-1,3 propane.Among the alkyl ether amines that may be mentioned as examples of specific compounds: 2-methoxy-ethylamine, 3-methoxy-propylamine, 4-methoxy-butylamine, 3-ethoxypropylamine, 3-octyloxy propylamine, decyloxy-3 propylamine, hexadecyloxy-3 propylamine, eicosyloxy-3 propylamine, docosyloxy-3 propylamine, N- (3-octyloxy-propyl) diamino-1,3 propane, N- (decyloxy- 3 propyl) diamino-1,3 propane, (trimethyl-2,4,6 decyl) oxy-3 propylamine and N- (trimethyl-2,4,6 decyl) oxy-3 propyl diamino-1,3 propane.

Le composé à fonction amine primaire mis en jeu dans la préparation des copolymères modifiés de l'invention peut aussi consister en un aminoalcool de formule (IV) :



        HO - R¹⁰ - NH₂



où R¹⁰ représente un radical aliphatique de préférence saturé, divalent, linéaire ou ramifié, de préférence sensiblement linéaire, ayant la définition donnée ci-avant.
On utilise de préférence des aminoalcools comportant une fonction alcool primaire.The compound with a primary amine function involved in the preparation of the modified copolymers of the invention may also consist of an amino alcohol of formula (IV):



HO - R¹⁰ - NH₂



where R¹⁰ represents an aliphatic radical preferably saturated, divalent, linear or branched, preferably substantially linear, having the definition given above.
Amino alcohols having a primary alcohol function are preferably used.

Comme composés spécifiques, on peut citer à titre d'exemples :
la monoéthanolamine, l'amino-1 propanol-3, l'amino-1 butanol-4, l'amino-1 pentanol-5, l'amino-1 hexanol-6, l'amino-1 heptanol-7, l'amino-1 octanol-8, l'amino-1 décanol-10, l'amino-1 undécanol-11, l'amino-1 tridécanol-13, l'amino-1 tétradécanol-14, l'amino-1 hexadécanol-16, l'amino-2 méthyl-2 propanol-1, l'amino-2 butanol-1 et l'amino-2 pentanol-1.As specific compounds, there may be mentioned as examples:
monoethanolamine, amino-1 propanol-3, amino-1 butanol-4, amino-1 pentanol-5, amino-1 hexanol-6, amino-1 heptanol-7, amino-1 octanol-8, amino-1 decanol-10, amino-1 undecanol-11, amino-1 tridecanol-13, amino-1 tetradecanol-14, amino-1 hexadecanol- 16, 2-amino-2-methyl-propanol-1, 2-amino butanol-1 and 2-amino pentanol-1.

Il doit être entendu qu'il est possible de mettre en jeu comme composé à fonction amine primaire un ou plusieurs composés répondant à la formule (III) et/ou un ou plusieurs composés répondant à la formule (IV).
Comme exemples spécifiques de mélange de composés à fonction amine primaire, on peut citer :

  • les coupes d'amines grasses primaires dont les chaînes alkyles comportent, en proportions molaires approximatives données dans le tableau ci-après des chaînes en C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ et C₂₂.
Figure imgb0008
 It should be understood that it is possible to bring into play as a compound with a primary amine function one or more compounds corresponding to the formula (III) and / or one or more compounds corresponding to formula (IV).
As specific examples of a mixture of compounds with a primary amine function, there may be mentioned:
  • cuts of primary fatty amines whose alkyl chains contain, in approximate molar proportions given in the table below, chains of C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ and C₂₂.
Figure imgb0008

La réaction d'addition du composé à fonction amine primaire sur le polyester insaturé est habituellement effectuée par simple chauffage à une température habituellement d'environ 25 à 200 °C, de préférence de 40 à 160 °C et par exemple à environ 60 °C. La réaction est effectuée par addition du composé à fonction amine primaire au polyester insaturé dissous dans un solvant choisi par exemple parmi ceux mentionnés ci-dessus, et chauffage, à la température choisie, pendant un temps suffisant pour que le réaction soit substantiellement complète. La durée de la réaction entre le composé à fonction amine primaire et le polyester insaturé est habituellement d'environ 1 à 24 heures et le plus souvent d'environ 2 à 10 heures et par exemple environ 3 heures. La quantité de composé à fonction amine primaire mise en réaction est habituellement de 0,2 à 1,5 mole, de préférence de de 0,4 à 1,2 mole et de manière la plus préférée de 0,5 à 1,1 mole par mole de composé dicarboxylique mis en jeu dans la formation du polyester insaturé. La quantité de composé à fonction amine est par exemple d'environ 1 mole pour 1 mole de composé dicarboxylique.The addition reaction of the compound with primary amine function on the unsaturated polyester is usually carried out by simple heating at a temperature usually of about 25 to 200 ° C, preferably from 40 to 160 ° C and for example at about 60 ° C . The reaction is carried out by adding the compound containing a primary amine function to the unsaturated polyester dissolved in a solvent chosen, for example, from those mentioned above, and heating, at the chosen temperature, for a time sufficient for the reaction to be substantially complete. The reaction time between the primary amine functional compound and the unsaturated polyester is usually about 1 to 24 hours and most often about 2 to 10 hours and for example about 3 hours. The quantity of compound with primary amine function reacted is usually from 0.2 to 1.5 mol, preferably from from 0.4 to 1.2 moles and most preferably from 0.5 to 1.1 moles per mole of dicarboxylic compound involved in the formation of the unsaturated polyester. The amount of amine-functional compound is, for example, about 1 mole per 1 mole of dicarboxylic compound.

Les polymères modifiés de la présente invention qui peuvent être avantageusement utilisés comme additifs dans les distillats moyens du pétrole sont ceux qui comportent des chaînes latérales pendantes sensiblement linéaires ayant au moins 8 atomes de carbone, de préférence au moins 10 atomes de carbone et d'une manière la plus préférée au moins 12 atomes de carbone, ladite chaîne pouvant comporter des atomes d'oxygène et/ou d'azote. Ces chaînes latérales peuvent provenir soit du composé époxydé utilisé dans la préparation du polyester insaturé, soit du composé à fonction amine primaire mis en réaction avec le polyester insaturé, soit à la fois du composé époxydé et du composé à fonction amine primaire.The modified polymers of the present invention which can be advantageously used as additives in petroleum middle distillates are those which have substantially linear pendant side chains having at least 8 carbon atoms, preferably at least 10 carbon atoms and of a most preferably at least 12 carbon atoms, said chain possibly comprising oxygen and / or nitrogen atoms. These side chains can come either from the epoxidized compound used in the preparation of the unsaturated polyester, or from the compound with primary amine function reacted with the unsaturated polyester, or from both the epoxidized compound and from the compound with primary amine function.

De préférence, les polymères modifiés selon l'invention utilisés comme additifs dans les distillats moyens sont ceux qui comportent des chaînes latérales pendantes ayant au moins 8 atomes de carbone et avantageusement au moins 10 atomes de carbone et d'une manière la plus préférée au moins 12 atomes de carbone, provenant à la fois du composé époxydé utilisé dans la préparation du polyester insaturé et du composé à fonction amine primaire mis en réaction avec la polyester insaturé.Preferably, the modified polymers according to the invention used as additives in middle distillates are those which have pendant side chains having at least 8 carbon atoms and advantageously at least 10 carbon atoms and most preferably at least 12 carbon atoms, originating both from the epoxidized compound used in the preparation of the unsaturated polyester and from the compound with a primary amine function reacted with the unsaturated polyester.

Les polymères modifiés selon l'invention ont habituellement une masse moléculaire en nombre d'environ 400 à 20 000 et de préférence d'environ 500 à 10 000 et le plus souvent d'environ 500 à 7 000.The polymers modified according to the invention usually have a number-average molecular weight of about 400 to 20,000 and preferably about 500 to 10,000 and most often about 500 to 7,000.

Les polymères modifiés préférés selon l'invention, tels qu'ils sont définis ci-dessus permettent d'avoir simultanément une amélioration du point de trouble et du point d'écoulement des distillats moyens de pétrole ce qui les rend particulièrement attractifs pour le raffineur.The preferred modified polymers according to the invention, as defined above, make it possible to simultaneously have an improvement in the cloud point and the pour point of petroleum middle distillates, which makes them particularly attractive to the refiner.

Les additifs sont obtenus en solution dans le solvant choisi et peuvent être utilisés sous cette forme directement dans les distillats moyens de pétrole (par exemple dans les gazoles) dont on souhaite améliorer le point d'écoulement et le point de trouble.The additives are obtained in solution in the chosen solvent and can be used in this form directly in petroleum middle distillates (for example in gas oils) for which it is desired to improve the pour point and the cloud point.

Pour observer une nette amélioration simultanée du point de trouble et du point d'écoulement des coupes de gazoles considérées dans l'invention, et définies ci-après, il est nécessaire d'ajouter ces additifs à des concentrations allant par exemple de 0,001 à 2 % en poids et de préférence de 0,01 à 1 % en poids et plus avantageusement de 0,02 à 0,3 % en poids.To observe a clear simultaneous improvement in the cloud point and the pour point of the gas oil cuts considered in the invention, and defined below, it is necessary to add these additives at concentrations ranging for example from 0.001 to 2 % by weight and preferably from 0.01 to 1% by weight and more advantageously from 0.02 to 0.3% by weight.

Les compositions de gazoles selon l'invention comprennent une proportion majeure de distillat moyen de pétrole ayant un intervalle de distillation selon la norme de distillation ASTM D 8667 se situant entre 150 et 450 °C (fuels-oils, gazoles) et une proportion mineure, suffisante pour en abaisser simultanément le point de trouble et le point d'écoulement, d'au moins un polymère modifié défini ci-avant.The gas oil compositions according to the invention comprise a major proportion of middle petroleum distillate having a distillation range according to the distillation standard ASTM D 8667 lying between 150 and 450 ° C. (fuels oils, gas oils) and a minor proportion, sufficient to lower the cloud point and the pour point simultaneously with at least one modified polymer defined above.

Les gazoles considérés plus particulièrement ont un intervalle de distillation allant d'une température initiale d'environ 160 à 190 °C à une température finale d'environ 360 à 430 °C.The gas oils considered more particularly have a distillation range from an initial temperature of about 160 to 190 ° C to a final temperature of about 360 to 430 ° C.

Les compositions de gazole comprenant une proportion majeure de distillat moyen et au moins un additif choisi parmi les polymères modifiés selon l'invention, définis ci-avant, en quantité suffisante pour en abaisser le point de trouble et le point d'écoulement, peuvent également comprendre d'autres additifs tels que par exemple des additifs antioxydants, des additifs dispersant les boues, des inhibiteurs de corrosion, etc...Diesel compositions comprising a major proportion of middle distillate and at least one additive chosen from the polymers modified according to the invention, defined above, in an amount sufficient to lower the cloud point and the pour point, may also include other additives such as for example antioxidant additives, additives dispersing sludge, corrosion inhibitors, etc.

Les compositions comprennent habituellement au moins 95 % et de préférence au moins 98 % en poids de distillat moyen.The compositions usually comprise at least 95% and preferably at least 98% by weight of middle distillate.

L'abaissement du point d'écoulement peut aller, par exemple jusqu'à 15 °C ou plus. En outre, on observe simultanément un abaissement du point de trouble pouvant aller, par exemple, jusqu'à 2 °C ou plus.The lowering of the pour point can go, for example up to 15 ° C or more. In addition, a decrease in the cloud point can simultaneously be observed, which can go, for example, up to 2 ° C. or more.

Les polymères modifiés utilisés dans l'invention permettent, par leur action sur les phénomènes cinétiques de cristallisation, en particulier des paraffines, et sur la modification de la taille des cristaux qui se forment, l'emploi de la suspension à une température plus basse sans bouchage des canalisations, ni colmatage des filtres.
Lorsque les cristaux de paraffines dont la formation est provoquée par le refroidissement sont apparus, leur tendance naturelle est de se rassembler par gravité dans la partie basse. Ce phénomène, connu sous le terme de sédimentation, provoque le bouchage des canalisations et le colmatage des filtres et est préjudiciable à la bonne utilisation des distillats moyens et notamment des gazoles et fuels domestiques à basse température. Les polymères modifiés de l'invention diminuent la vitesse de sédimentation des paraffines formées par refroidissement des gazoles et autres distillats moyens ; les paraffines restant davantage en suspension se déposent moins sur les parois des conduites en contact avec les gazoles et autres distillats moyens, retardant ainsi le bouchage desdites conduites, et permettant d'utiliser un produit de caractéristiques données à une température nettement plus basse ou d'employer à une température donnée un produit, qui obtenu par la raffineur sans modification du schéma de distillation n'a pas initialement les spécifications requises ; spécifications qui évoluent actuellement dans le sens d'une plus grande sévérité.The modified polymers used in the invention allow, by their action on the kinetic phenomena of crystallization, in particular paraffins, and on the modification of the size of the crystals which form, the use of the suspension at a lower temperature without clogging of pipes, or clogging of filters.
When the paraffin crystals whose formation is caused by cooling have appeared, their natural tendency is to collect by gravity in the lower part. This phenomenon, known under the term sedimentation, causes the clogging of the pipes and the clogging of the filters and is detrimental to the proper use of middle distillates and in particular of domestic diesel and fuels at low temperature. The modified polymers of the invention reduce the rate of sedimentation of the paraffins formed by cooling the gas oils and other middle distillates; the paraffins remaining more in suspension are deposited less on the walls of the pipes in contact with gas oils and other middle distillates, thus delaying the clogging of said pipes, and making it possible to use a product of given characteristics at a significantly lower temperature or using a product at a given temperature, which obtained by the refiner without modifying the distillation scheme does not initially have the required specifications; specifications which are currently evolving in the direction of greater severity.

Les exemples suivants illustrent l'invention sans en limiter la portée.
Dans les exemples, les coupes de gazoles utilisées sont celles qui figurent au tableau II ; elles sont caractérisées d'après la distillation ASTM D 8667, ces coupes de gazoles d'origine ARAMCO sont désignées par G₁ et G₂ ; leur masse volumique est également indiquée sur le tableau II.The following examples illustrate the invention without limiting its scope.
In the examples, the gas oil cuts used are those which appear in Table II; they are characterized according to the distillation ASTM D 8667, these cuts of diesel oils of ARAMCO origin are designated by G₁ and G₂; their density is also indicated in Table II.

Pour les coupes G₁ et G₂ sans additif et pour les compositions contenant un additif, deux déterminations ont été effectuées :

  • le point de trouble suivant la norme ASTM D 2500-66
  • le point d'écoulement suivant la norme ASTM D97-66.
Figure imgb0009
 For cuts G₁ and G₂ without additive and for compositions containing an additive, two determinations were made:
  • the cloud point according to ASTM D 2500-66
  • the pour point according to ASTM D97-66.
Figure imgb0009

Exemple 1 (comparatif) Example 1 (comparative)

On introduit dans un réacteur de 250 ml muni d'un réfrigérant et d'un système d'agitation, 14,7 g (0,15 mole) d'anhydride maléique, 19,5 g (0,15 équivalent molaire) de n-butoxy-1 époxy-2,3 propane et 17,6 g de xylène. On porte à 60 °C, puis on introduit 0,51 g de titanate de n-butyle et on maintient le mélange à 60 °C pendant 14 heures tout en agitant. On obtient un polyester insaturé sous forme d'un produit jaune qui peut être caractérisé par les moyens classiques d'analyse ; son spectre IR montre la disparition des bandes dues à l'anhydride maléique à 1850 cm⁻¹ et 1780 cm⁻¹ et l'apparition d'une forte bande ester à 1720 cm⁻¹.14.7 g (0.15 mole) of maleic anhydride, 19.5 g (0.15 molar equivalent) of n are introduced into a 250 ml reactor equipped with a condenser and a stirring system. -butoxy-1 epoxy-2,3 propane and 17.6 g of xylene. It is brought to 60 ° C., then 0.51 g of n-butyl titanate is introduced and the mixture is kept at 60 ° C. for 14 hours while stirring. An unsaturated polyester is obtained in the form of a yellow product which can be characterized by conventional means of analysis; its IR spectrum shows the disappearance of the bands due to maleic anhydride at 1850 cm⁻¹ and 1780 cm⁻¹ and the appearance of a strong ester band at 1720 cm⁻¹.

Le polymère obtenu est dilué à 50 % en poids dans du xylène ; cette solution constitue la solution mère de l'additif A.The polymer obtained is diluted to 50% by weight in xylene; this solution constitutes the mother solution of additive A.

Exemples 2 à 4Examples 2 to 4

On prépare de la même manière que dans l'exemple 1 la même solution du même polyester que celui décrit dans l'exemple 1 et on procède sur diverses parts de ce polyester insaturé à l'addition de composés présentant des fonctions amines primaires.The same solution of the same polyester as that described in Example 1 is prepared in the same manner as in Example 1 and the procedure is carried out on various parts of this unsaturated polyester to the addition of compounds having primary amine functions.

Exemple 2Example 2

Dans le réacteur contenant le polyester insaturé, dissous dans le xylène, on ajoute 42 g (0,15 équivalent molaire d'amine primaire) d'une coupe d'amines grasses primaires dont les chaines alkyles comportent en moyenne en moles 1 % de C₁₄, 28 % de C₁₆ et 71 % de C₁₈. Après 3 heures de chauffage à 60 °C tout en agitant, on obtient une solution d'un produit qui après évaporation du solvant peut être caractérisé par les moyens classiques d'analyse : sa masse moléculaire moyenne en nombre est de 6500, sa polydispersité est de 1,2 (mesurées par Chromatographie d'Exclusion Stérique (C.E.S)), le spectre R.M.N. montre la disparition de l'insaturation et confirme l'addition de l'amine sur la double liaison ; en spectrométrie infrarouge on note également la disparition de la bande correspondant à l'insaturation éthylénique du polymère de départ.
La solution obtenue est diluée de façon à obtenir une solution à 50 % en poids dans le xylène, du produit, qui constitue la solution mère de l'additif A1.In the reactor containing the unsaturated polyester, dissolved in xylene, 42 g (0.15 molar equivalent of primary amine) of a cut of primary fatty amines are added, the alkyl chains of which contain on average 1% of C₁₄ in moles , 28% of C₁₆ and 71% of C₁₈. After 3 hours of heating at 60 ° C. while stirring, a solution of a product is obtained which, after evaporation of the solvent, can be characterized by conventional means of analysis: its number average molecular mass is 6,500, its polydispersity is 1.2 (measured by Steric Exclusion Chromatography (CES)), the NMR spectrum shows the disappearance of the unsaturation and confirms the addition of the amine to the double bond; in infrared spectrometry, the disappearance of the band corresponding to the ethylenic unsaturation of the starting polymer is also noted.
The solution obtained is diluted so as to obtain a 50% by weight solution in xylene, of the product, which constitutes the mother solution of the additive A1.

Exemple 3Example 3

La coupe d'amines grasses primaires additionnée au polyester est constituée d'amines primaires dont les chaines alkyles comprennent environ en moles 3 % de C₈ , 6 % de C₁₀, 56 % de C₁₂ , 18 % de C₁₄, 10 % de C₁₆, 2 % de C₁₈, et 5 % de C₁₈ insaturé. Le mode opératoire est en tous points itdentique à celui décrit dans l'exemple 2.
Les spectres IR et RMN du produit présentent les mêmes bandes caractéristiques que celles de l'additif A1. On obtient ainsi une solution de l'additif A2. L'additif A2 a une masse moléculaire moyenne en nombre de 4 700 et sa polydispersité est de 1,33 (mesurées par C.E.S.).The cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles 3% of C₈, 6% of C₁₀, 56% of C₁₂, 18% of C₁₄, 10% of C₁₆, 2 % of C₁₈, and 5% of unsaturated C₁₈. The operating mode is in all respects identical to that described in Example 2.
The IR and NMR spectra of the product have the same characteristic bands as those of the additive A1. A solution of the additive A2 is thus obtained. Additive A2 has a number average molecular weight of 4,700 and its polydispersity is 1.33 (measured by CES).

Exemple 4Example 4

La coupe d'amines grasses primaires additionnée au polyester est constituée d'amines primaires dont les chaines alkyles comprennent environ en moles 1 % de C₁₄, 5 % de C₁₆, 42 % de C₁₈, 12 % de C₂₀ et 40 % de C₂₂. Le mode opératoire est en tous points identique à celui décrit dans l'exemple 2. Les spectres IR et RMN du produit présentent les mêmes bandes caractéristiques que celles de l'additif A1. On obtient ainsi une solution de l'additif A3. L'additif A₃ une masse moléculaire moyenne en nombre de 6 300 et sa polydispersité est de 1,2 (mesurées par C.E.S).The cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles 1% of C₁₄, 5% of C₁₆, 42% of C₁₈, 12% of C₂₀ and 40% of C₂₂. The procedure is identical in all respects to that described in Example 2. The IR and NMR spectra of the product have the same characteristic bands as those of the additive A1. A solution of the additive A3 is thus obtained. Additive A₃ has a number average molecular weight of 6,300 and its polydispersity is 1.2 (measured by C.E.S).

Exemple 5 (comparatif) Example 5 (comparative)

On prépare de la même manière que dans l'exemple 1 un polyester insaturé qui diffère de celui de l'exemple 1 en ce que l'on emploie une coupe d'époxystéarate d'hexadécyle comme composé époxydé. Cette coupe a été obtenue par époxydation d'oléine (mélange d'acides gras insaturés dont la composition moyenne en poids est donnée dans le tableau I du texte de la présente demande) puis estérification du mélange d'époxy-acides obtenu par un mélange d'alcools comprenant en proportions pondérales approximatives 95 % d'alcool n-hexadécylique, 3 % d'alcool n-octadécylique et 2 % d'alcool ayant plus de 18 atomes de carbone dans leur molécule. On obtient après dilution à 50 % en poids dans du xylène une solution de l'additif B.An unsaturated polyester is prepared in the same manner as in Example 1, which differs from that of Example 1 in that a cut of hexadecyl epoxystearate is used as the epoxidized compound. This section was obtained by epoxidation of olein (mixture of unsaturated fatty acids whose average composition by weight is given in table I of the text of the present application) then esterification of the mixture of epoxy-acids obtained by a mixture of 'Alcohols comprising in approximate weight proportions 95% of n-hexadecyl alcohol, 3% of n-octadecyl alcohol and 2% of alcohol having more than 18 carbon atoms in their molecule. After diluting to 50% by weight in xylene, a solution of additive B is obtained.

Exemples 6 à 9 : Examples 6 to 9 :

On prépare de la même manière que dans l'exemple 5 la même solution du même polyester que celui décrit dans l'exemple 5 et on procède sur diverses parts de ce polyester insaturé à l'addition de composés présentant des fonctions amines primaires, en suivant le mode opératoire décrit dans l'exemple 2 et en respectant les proportions molaires de l'exemple 2. Les spectres infrarouge et R.M.N confirment la structure des produits et en particulier l'addition des composés aminés primaires sur la double liaison.The same solution is prepared in the same manner as in Example 5, the same polyester as that described in Example 5, and various compounds of this unsaturated polyester are added to the compounds having primary amine functions, following the procedure described in Example 2 and respecting the molar proportions of Example 2. The infrared and NMR spectra confirm the structure of the products and in particular the addition of the primary amino compounds to the double bond.

Exemple 6Example 6

L'amine primaire additionnée au polyester est la n-octadécylamine. On obtient ainsi une solution de l'additif B1.The primary amine added to the polyester is n-octadecylamine. A solution of the additive B1 is thus obtained.

Exemple 7Example 7

La coupe d'amines grasses primaires additionnée au polyester est constituée d'amines primaires dont les chaines alkyles comprennent environ en moles :1 % de C₁₄, 28 % de C₁₆ et 71 % de C₁₈. On obtient ainsi une solution de l'additif B2. L'additif B2 a une masse moléculaire moyenne en nombre de 2 800 et sa polydispersité est de 1,65 (mesurées par C.E.S.)The cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles: 1% of C₁₄, 28% of C₁₆ and 71% of C₁₈. A solution of the additive B2 is thus obtained. Additive B2 has a number average molecular weight of 2,800 and its polydispersity is 1.65 (measured by C.E.S.)

Exemple 8Example 8

La coupe d'amines grasses primaires additionnée au polyester est constituée d'amines primaires dont les chaines alkyles comprennent environ : 3 % de C₈, 6 % de C₁₀, 56 % de C₁₂, 18 % de C₁₄, 10 % de C₁₆, 2 % de C₁₈ et 5 % de C₁₈ insaturé. On obtient ainsi une solution de l'additif B3. L'additif B3 a une masse moléculaire moyenne en nombre de 2600 et sa polydispersité est de 1,72 (mesurées par C.E.S.).The cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately: 3% of C₈, 6% of C₁₀, 56% of C₁₂, 18% of C₁₄, 10% of C%, 2% of C₁₈ and 5% of unsaturated C₁₈. A solution of the additive B3 is thus obtained. Additive B3 has a number average molecular weight of 2600 and its polydispersity is 1.72 (measured by C.E.S.).

Exemple 9Example 9

La coupe d'amines grasses primaires additionnée au polyester est constituée d'amines primaires dont les chaines alkyles comprennent environ en moles : 1 % de C₁₄, 5 % de C₁₆, 42 % de C₁₈, 12 % de C₂₀ et 40 % de C₂₂. On obtient ainsi une solution de l'additif B4. L'additif B4 a une masse moléculaire moyenne en nombre de 2 200 et sa polydispersité est de 2,15 (mesurées par C.E.S.).The cut of primary fatty amines added to the polyester consists of primary amines whose alkyl chains comprise approximately in moles: 1% of C₁₄, 5% of C₁₆, 42% of C₁₈, 12% of C₂₀ and 40% of C₂₂. A solution of the additive B4 is thus obtained. Additive B4 has a number average molecular weight of 2,200 and its polydispersity is 2.15 (measured by C.E.S.).

Les additifs décrits ci-dessus sont obtenus en solution dans le xylène. La concentration des solutions est ajustée à 50 % poids de matière sèche, ce qui fournit les solutions mères de ces additifs dont on test l'activité en les incorporant à raison de 0,1 % en poids par rapport au gazole dont les caractéristiques ont été données dans le tableau II ci-avant.The additives described above are obtained in solution in xylene. The concentration of the solutions is adjusted to 50% by weight of dry matter, which provides the stock solutions of these additives, the activity of which is tested by incorporating them at a rate of 0.1% by weight relative to the diesel fuel, the characteristics of which have been given in table II above.

Les résultats de ces déterminations sont rassemblés dans le tableau III ci-après. Ils montrent nettement l'amélioration simultanée du point de trouble et du point d' écoulement que permettent d'obtenir les polymères modifiés selon l'invention par rapport à un gazole sans additif et par rapport à l'emploi d'un polyester insaturé (A ou B) non modifié (exemple comparatif). TABLEAU III Additifs % poids Point de trouble (°C) Point d'écoulement (°C) G1 G2 G1 G2 néant - 1 - 2 - 9 - 9 0,1 % A - 1 - 2 - 9 - 9 0,1 % A1 - 2 - 3 - 12 - 12 0,1 % A2 - 3 - 3 - 15 - 18 0,1 % A3 - 3 - 4 - 12 - 12 0,1 % B - 1 - 2 - 9 - 9 0,1 % B1 - 3 - 4 - 12 - 12 0,1 % B2 - 3 - 4 - 12 - 12 0,1 % B3 - 2 - 3 - 24 - 24 0,1 % B4 - 3 - 4 - 15 - 12 The results of these determinations are collated in Table III below. They clearly show the simultaneous improvement in the cloud point and the pour point which the polymers modified according to the invention make it possible to obtain with respect to an additive-free gas oil and with respect to the use of an unsaturated polyester (A or B) unmodified (comparative example). TABLE III % By weight additives Cloud point (° C) Pour point (° C) G1 G2 G1 G2 nil - 1 - 2 - 9 - 9 0.1% A - 1 - 2 - 9 - 9 0.1% A1 - 2 - 3 - 12 - 12 0.1% A2 - 3 - 3 - 15 - 18 0.1% A3 - 3 - 4 - 12 - 12 0.1% B - 1 - 2 - 9 - 9 0.1% B1 - 3 - 4 - 12 - 12 0.1% B2 - 3 - 4 - 12 - 12 0.1% B3 - 2 - 3 - 24 - 24 0.1% B4 - 3 - 4 - 15 - 12

Claims (9)

  1. Polymer of average molecular weight ranging from 400 to 20 000 comprising amino-substituted groups in its molecule wherein it results from reaction of at least compound with a primary amine function, comprising 1 to 61 carbon atoms in its molecule and having one of the general formulae:
    Figure imgb0013
        and



            HO - R¹⁰ - NH₂   (IV)



    in which R⁹ represents an aliphatic group having 1 to 60 carbon atoms, Z is chosen from the groups -O-, -NH-, -NR¹¹-, in which R¹¹ represents an aliphatic group having 1 to 60 carbon atoms, n is a whole number from 2 to 4, m is zero when Z is -NH- or a whole number from 1 to 4 in all cases, R¹⁰ represents a bivalent aliphatic group having 2 to 61 carbon atoms, with an unsaturated polyester resulting from the condensation of at least one unsaturated dicarboxylic compound comprising at least one ethylenic unsaturation in the alpha position of one of the carboxyl groups with at least one epoxidated compound having 4 to 62 carbon atoms and having one of the general formulae
    Figure imgb0014
     in which R¹ and R³, identical or different, each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, R² represents a hydrogen atom, an alkyl group having 1 to 57 carbon atoms or an aliphatic group comprising 1 or more oxirane cycles and having 3 to 57 carbon atoms, R⁴ represents an alkylene group having 1 to 57 carbon atoms, R⁵ represents an alkyl group having 1 to 57 carbon atoms or an alkanoyl group of formula
    Figure imgb0015
     R⁶ in these formulae representing an alkyl group having 1 to 56 carbon atoms, the epoxidated compound/dicarboxylic compound molar ratio being from about 0.4:1 to 1.8:1 and the compound with a primary amine function/dicarboxylic compound molar ratio being from about 0.2:1 to 1.5:1.
  2. Polymer according to claim 1 wherein the dicarboxylic compound is chosen from the anhydrides of mono-unsaturated dicarboxylic acids having 4 to 8 carbon atoms in their molecule.
  3. Polymer according to claim 1 or 2 wherein the epoxidated compound is a compound having one of the general fomulae (I) or (II), in which R¹ and R³ each represent a hydrogen atom.
  4. Polymer according to claim 1 or 2 wherein the epoxidated compound is a compound having one of the general fomulae (I) or (II), in which R¹, R² and R³ each represent a hydrogen atom.
  5. Polymer according to one of claims 1 to 4 wherein the epoxidated compound is a compound of general formula (I), in which R⁴ is a methylene group.
  6. Polymer according to one of claims 1 to 4 wherein the epoxidated compound is a compound of general formula (II), in which R⁴ is an alkylene group having 4 to 24 carbon atoms.
  7. Polymer according to one of claims 1 to 6 wherein the compound with a primary amine function is a substantially linear primary monoalkylamine having 6 to 46 carbon atoms.
  8. Petroleum middle distillate composition comprising a major proportion of middle distillate having a distillation range between 150 and 450° C and a proportion, from 0.001 to 2% in weight of at least one polymer according to one of claims 1 to 7, said polymer comprising substantially linear side chains having at least 8 carbon atoms.
  9. Middle distillate composition according to claim 8 wherein the middle distillate consists of a gas oil cut having a distillation range from an initial temperature of about 160 to 190° C to a final temperature of about 360 to 430° C.
EP89400181A 1988-02-03 1989-01-23 Polymers derived from unsaturated polyesters by addition of compounds having an amine function, and their use as additives to modify the properties in the cold state of middle distillates of petroleum Expired - Lifetime EP0327423B1 (en)

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